Cyclopropanecarboxylic acid esters

ABSTRACT

Novel cyclopropanecarboxylic acid esters having an excellent insecticidal activity and harmless property to mammals and cattles, of the formula WHEREIN Y is oxygen or sulfur atom, R1 is hydrogen atom or methyl group, R2 is methyl, 2-methyl-1-propenyl, 2methoxycarbonyl-1-propenyl, phenyl or 3,4-methylenedioxyphenyl group when R1 is hydrogen atom, or methyl group when R1 is methyl group, R3 and R4 are same or different and are a halogen atom or methyl group, and m and n are 0 or an integer of 1 to 3, and the carboxylic acid ester is prepared by esterifying the derivatives of corresponding phenoxybenzyl or phenylthiobenzyl compounds with the carboxylic acids or their derivatives.

United States Patent Itaya et al.

[ CYCLOPROPANECARBOXYLIC ACID ESTERS [72] Inventors: Nobushige Itaya, Minoo-shi; Katsuzo Kamoshlta, Toyonaka-shi; Toshlo Mizutani, Hirakata-shi; Shigeyoshi Kitamura, Toyonaka-shi; Shinjl Nakai; Nobuyukl Kameda, both of Takarazuka-shi; Keimi Fujimoto, Higashiyama-ku, Tyoto; Yositosi Okuno, Toyonaka-shi, all of Japan [73] Assignee: Sumitomo Chemical Company, Ltd.,

Osaka, Japan [22] Filed: May 21, 1969 211 App]. No.: 827,490

[52] US. Cl ..260/468, 260/340.5, 260/469, 424/305 [51 Int. Cl ..C07c 69/00 [58] Field of Search ..260/468 P 56] References Cited UNITED STATES PATENTS 3,509,180 4/ 1970 Elliott ..260/468 FOREIGN PATENTS OR APPLICATIONS 1,926,433 12/1969 Germany ..260/468 51 3,666,789 51 May 30, 1972 Primary Examiner-Alex Mazel Assistant Examiner-James H. Tumipseed Attorney-Stevens. Davis, Miller & Mosher ABSTRACT Novel cyclopropanecarboxylic acid esters having an excellent insecticidal activity and harmless property to mammals and cattles, of the formula 9 Claims, No Drawings CYCLOPROPANECARBOXYLIC ACID ESTERS the production thereof. The present invention further relates 5 to an insecticidal composition containing said novel ester.

PRIOR ART As an insecticide having insect-knock-down and killing ability as well as harmless property to mammals and cattles, there have been hitherto used pyrethrum extracts including pyrethrin, and is sold on market recently a synthetic insecticide such as allethrin which is a homologue of pyrethrin and; 3 ,4,5 ,6-tetrahydrophthalimidomethyl chrysanthemate (referred to as ftetramethrin hereinafter). However, none of them satisfies at present time all of the desired conditions, showing drawback in some points and advantage in the other.

After studying to obtain new effective esters, the inventors have found a new type ester which is remarkably excellent in insecticidal activity as compared with the above pyrethrin and its homologue and is prepared at low costs. Thus, the present invention is achieved.

OBJECT An object of the present invention is to provide a new carboxylic acid ester having more excellent insecticidal activity at low costs.

CHEMICAL COMPOUNDS According to the present invention, a novel cyclopropanecarboxylic acid ester is provided, said ester having the following formula wherein Y is oxygen or sulfur atom; R, is hydrogen atom or 15 methyl group, R is methyl, 2-methyl-l-propenyl, 2-'methox- 20 ofl to 3.

It will be appreciated that the novel ester of the formula (I) includes naturally its optically active isomers which occur due to the asymmetric carbon atom possibly present in the carboxylic acid moiety such as d-trans-c'rysanthemum-monocarbox- 25 ylic acid residue.

Among the esters represented by the fonnula (l), the especially useful ones that are not limitative in the present invention, are enumerated as follows:

Compound Number Structure 0 H2O C HC C H;

CH=C

3-phenoxybenzyl chrysanthemate.

4-phenoxybenzyl chrysanthemate.

2-phen0xybenzyl chrysanthemate.

3-phen0xybenzyl 2, 2, 3, 3-tetramethylcyclopropanecarboxylate.

4-phenoxybenzyl 2, 2, 3, 3-tetra1nethylcyclopropanecarboxylate.

cmoc-oH-c on,

c CH=C cm on, 000011,

B-phenoxybenzyl pyrethrute.

9 10 123 :1 19)? Structure (32) 7 V CllzOC-CII-CIICH=C (a: +6 i X C...

CH CH;

C If;

3-o-tolylthiobenzyl chrysanthemate.

CHzO CCHCHCH=C G O CH: cfi. CH:

3-p-chlorophenylthiobenzyl chrysanthemate.

U SE OF THE COMPOUND I 20 out inaniriert solv it such as benzene, petroleum ether,

The cyclopropanecarboxylic acid ester of formula (I) has an excellent activity for killing insects such as houseflies, mosquitoes, cockroaches and the like, and can be used not only in a wide scope of the prevention of epidemics but also controlling insects injurious to stored cereals, agriculture, especially crops before harvest, household horticulture, green-house cultivation and food-packaging, without anxiety due to its low toxicity.

PROCESS FOR PRODUCTION OF COMPOUND The carboxylic acid ester of formula (I) is prepared for the first time by the present inventors, and is obtained easily and in good yield, for example, by method comprising reacting a diphenylether derivative of the formula CHzA wherein Y, R R, and m and n are same as defined above, and A is a halogen atom or hydroxy or tosyloxy group, with a cyclopropane carboxylic acid of the formula mo cH, 111) wherein R and R are same as defined above, or its reactive derivatives, in the presence of suitable reaction-auxiliary agent, if necessary.

The diphenylether derivative of formula (II) used in the method of the present invention is selected in such a relation of the other reactant, cyclopropane carboxylic acid and its reactive derivatives of formula (III) as to enable it to be subjected to esterification. The reactive derivatives of the carbox-v ylic acid of formula (III) means corresponding acid halide, acid anhydride, lower alkyl ester or salt. The following disclosure will explain more particularly the method of the preparation of the cyclopropanecarboxylic acid ester of formula (I) according to the present invention.

The first embodiment of the method is to obtain the objective ester by reacting as the diphenyl ether derivative an alcohol of the formula OHgOH containing a dehydrating agent such as dicyclohexylcarbodiimide with or without heating.

When the acid halide is used, the reaction is effected well at the room temperature in the presence of an'organic tertiary amine such as pyridine, triethylamine and the like as a dehydrogen halide agent. The acid halide used may be any ones, but acid chloride is usually used. in the reaction, the use of solvents is preferable to allow the reaction to proceed smoothly, and an inert solvent such as benzene, toluene and petroleum benzine is preferably used.

When the acid anhydride is used as'the reactant, the reac tion can proceed without any reaction-auxiliary agent well at the room temperature to form thejobjec'tive ester of formula (I). The warming of the reaction system and the use of solvents are favourable for allowing reaction to proceed smoothly, but they are not always indispensable.

When the lower alkyl ester is used as the reactant, the reaction is completed in the presence of a basic catalyst such as sodium alkoxide under heating condition, and proceeds smoothly by the use of an inert solvent such as benzene, toluene and the like. The preferable lower alkyl ester used in the present method includes methyl ester, ethyl ester, n-propyl ester, isopropyl ester and n-butyl ester, of the cyclopropanecarboxylic acid of formula (III).

The second embodiment of the process of the present invention is to prepare the objective ester of formula (I) from halides of the diphenyl ether of the formula CHQX wherein X is a halogen atom, and Y, R R and m and n are same as defined above. The another reactant is the salts of the carboxylic acid of formula (III) with alkali metals or tertiary amines, which salts may be formed in situ in the reaction by adding the corresponding bases forming such salts to the reaction mixture. The reaction is preferably carried out in the presence of an inert solvent such as benzene, acetone and the like at a temperature of the boiling point or the lower of the solvents for allowing the reaction to proceed. Among the halogen atoms presented by X in formula (V), chlorine or bromine atom is, in general, common, but other halogen atoms may be selected optionally.

The third embodiment of the method of the present invention is to obtain the objective ester of formula (I) from a tosylates of the diphenyl ether of the formula wherein Y, R R and m and n are same as defined above. in this case, the another reactant is those same as used in the W103i man second embodiment, and the reaction condition is also same as that used therein.

STARTING MATERIALS The cyclopropanecarboxylic acids of formula (III) used as the reactant according to the present invention can be prepared by already known process, and, if necessary, may be converted to each of the reactive derivatives according to well known method. The alcohols represented by formula (IV) are easily prepared by reducing corresponding carboxylic acid ester or hydrolyzing corresponding halides of formula (V) and the halides may be prepared with good yield by halogenating the side chain of corresponding toluenes. The tosylates of formula (VI) may also easily be prepared by reacting the alcohols of formula (IV) with p-toluene sulfonyl chloride.

It will be appreciated that the carboxylic acid of formula (III) and its derivatives may include optically active isomers, such as d-trans-chrysanthemic acid and reactive derivatives thereof.

INSECT ICIDAL COMPOSITION In the preparation of insecticidal compositions, the new esters of formula (I) may be formulated into any desired forms of oil sprays, emulsifiable concentrates, dusts, wettable powders, aerosols, mosquito coils, fumigants, granules, baits and luring dust or solid preparation, according to known method in the art applied to the pyrethrum extracts, allethrin and the like, using auxiliary agents and/or carriers for common insecticidal compositions, although the solution of the ester in organic solvent such as xylene and methylnaphthalene is sometimes convenient.

The insecticidal compositions thus formed may be increased in its activity when used in admixture with a synergist for pyrethroid such as 3,4-methylenedioxy-6-propylbenzylbutyldiethylene glycolether (hereinafter referred to as piperonylbutoxide"), l ,2-methylenedioxy-4-[ 2-( octylsulfinyl)-propyl ]-benzene (hereinafter referred to as sulfoxide), N-(2-ethylhexyl)-bicyclo[2,2, l jhepta-5-ene-2,3-dicarboximide (hereinafter referred to as MGK-264, registered trade name for said imide produced by McRolin Gorrnley King Co.), N-(4-pentynyl)-phthalimide or o-n-propyl-O-propargylphenyl phosphonate. (hereinafter referred to NlA-l6388). When the present compounds are formulated into mosquito coils, the activity can be increased by incorporation of a known additive therefor, such as terephthalic or isophthalic acid and butyl hydroxytoluene (referred to as BHT). In addition, the. present compounds may be formulated into multipurpose compositions by incorporation of other active ingredients such as pyrethroids, for example, pyrethrum extracts, allethrin, tetramethrin, 5-benzyl-3-furylmethyl chrysanthemate; organic chloride insecticides, for example, dichlorodiphenyltrichloromethane (referred to as DDT), benzene hexachloride (referred-to as Bl-IC) and methoxychlor; organic phosphor insecticides, for example, 0,0- dimethyl 3-methyl-4-nitrophenyl) phosphorothioate (hereinafter referred to as Fenitrothion), 0,0-dimethyl 0- 2,2-dichlorovinyl) phosphate (referred to as DDVP"); carbamate type'insecticides, for example, l-naphthyl-N-methylcarbamate and 3,4-xylyl-N-methylcarbamate; or other insecticides, fungicides, acaricides, herbicides, fertilizers or other agricultural chemicals.

The present invention will be more particularly illustrated by the following Examples which should not restrict the invention defined in the attached claims.

EXAMPLES l 34 Production of the Cyclopropanecarboxylic Acid Esters The esters of the present invention shown in Table l were produced by standard processes each represented by A, B, C, D, E and F as follows: Process A The Reaction of the Alcohol of the Formula (IV) with the Carboxylic Acid Halide.

In a solution of 0.05 mol. of the alcohol in 3 times by volume of dry benzene 0.075 mol. of pyridine is added. To the solution, there is added a solution containing 0.053 mol. of the carboxylic acid chloride in its 3 times by volume of dry benzene at a time to react under generation of heat. After allowed to stand over a night with tightly sealing, the reaction mixture is added with a slight amount of water to dissolve pyridine hydrochloride precipitation, and the aqueous layer formed is removed. The organic layer is successively washed with an aqueous solution containing 5 percent by weight of hydrochloric acid and a saturated aqueous solution of sodium hydrogencarbonate, and a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate, and distilled to remove benzene. The residual liquid is subjected to silica gel chromatography to recover the purified objective ester in the form of pale yellow oil.

Process B The Dehydration Reaction between the Alcohol of Formula (IV) with the Carboxylic Acid of Formula (III).

To a solution of 0.05 mol. each of the alcohol and the carboxylic acid in 3 times by volume of benzene, 0.08 mol. of dicyclohexylcarbodiimide is added while stirring, and the reaction mixture is allowed to stand over a night, with tightly sealing. Next day, the reaction is completed by refluxing for 2 hours, and then the objective ester is recovered by the procedures same as described in Process A.

Process C The Reaction of the Alcohol of Formula IV) with the Carboxylic Acid Anhydride.

To a solution of 0.05 mol. of the alcohol in 3 times by volume of toluene, 0.055 mol. of the carboxylic acid anhydride prepared by reaction of the carboxylic acid of formula (III) with acetic anhydride, is added, heated at C. for 3 hours to complete the reaction. After cooled, the reaction mixture is neutralized with 10 per cent aqueous solution of sodium hydroxide at a temperature of not higher than 10 C. and the carboxylic acid resulted from the reaction is recovered as sodium salt thereof from the aqueous layer. The organic layer is treated by the procedure same as described in Process A, and the objective ester is thus obtained.

Process D The Ester Interchange Reaction between the Alcohol of Formula (IV) with the Lower Alkyl Ester of the Carboxylic Acid.

To a solution of 0.06 mol. of ethyl ester of the carboxylic acid of formula (III) and 0.05 mol. of the alcohol in 5 times by volume of dried toluene, 0.005 mol. of sodium ethoxide is added. The reaction system is well stirred and refluxed for 10 hours to complete the reaction, while removing the formed ethanol as azeotropic mixture from the top of the rectification column. After adding water carefully, the objective ester is recovered from the organic layer by the procedures same as described in Process A.

Process E The Reaction of the Halide of Formula (IV) with the Carboxylic Acid of Formula (III).

A solution of 0.05 mol. of the halide and 0.06 mol. of the carboxylic acid in 3 times by volume of acetone is warmed at 15 to 20 C., and is added dropwise with a solution of 0.08 mol. of triethylamine in 3 times of volume of acetone over a time of 1 hour while stirring. After the addition, the reaction system is refluxed for 2 hours to complete the reaction and cooled. The precipitating triethylamine hydrochloride is filtered off. The filtrate is distilled to remove acetone. Three times by volume of benzene is added to the remaining liquid. The organic layer is treated by the procedures same as described in Process A, to obtain the objective ester.

Process F The Reaction of the Tosylate of Formula (V1) with Salt of the Carboxylic Acid of Formula (III).

To a solution of 0.05 mol. of the tosylate in 3 times by volume of acetone, 0.06 mol. of the sodium carboxylate which has been prepared by reacting the carboxylic acid and sodium hydroxide in water and distilling off water to obtain a dry mass, is added at a room temperature over a time of 30 minutes while stirring. The reaction system is refluxed for 30 minutes to complete the reaction, and cooled. A precipitation formed is filtered off, and the filtrate is distilled to remove the acetone. The remaining is dissolved in 3 times by volume of benzene, and the objective ester is recovered from the organic liquid by the procedures as described in Process A.

According to the above-mentioned standard processes, resulting esters are each shown in the following Table 1 from the starting materials which are also shown therein.

Table 1 Continued 2 Preparation of insecticidal Composition and Test Data thereof The ester used is represented by the compound number previously mentioned, and parts are by weight.

EXAMPLE 35 0.05 part of the present compounds (1), (4) and (6), respectively, was dissolved in kerosene to make 100 parts.

Three oil spray were thus obtained.

Found EXAMPLE 36 0.2 part of the present compounds (2), (5), (7), (8) and (10), respectively, and 0.8 part of piperonyl butoxide were dissolved in kerosene to make 100 parts. Five oil sprays containing 0.2 per cent by weight of the present compounds and 0.8 per cent by weight of a synergist, butoxide, were thus obtained, respectively.

Elementary analysis (percent) Calculated Refractive index EXAMPLE 37 Theorctical yield cent) Yielding cyclopropanecarboxylic ester EXAMPLE 38 EXAMPLE 39 0.6 g of the present compounds (1), (4), (5), (6), and dtrans-chrysanthemate of l) and (19), respectively, were dissolved in 20 ml of methanol. The solutions were homogeneously mixed with 99.4 g of a mosquito coil carrier consisting of a mixture of Tabu powder, Pyrethrum mare and wood powder in the ratio of 3 5 l, and methanol is evaporated. The remainings were added with lSO ml. of water, kneeded thoroughly, and shaped into mosquito coils and dried. Thus, six mosquito coils each containing 0.6 per cent of the active compound were thus obtained, respectively.

Proc ess Compound 3-m-tolylthiobenzylchrysanthemate. A 3 o-tolylthiobcnzylcln'ysanthemate. 34 3-p-chlorophenylthiobenzyl Ethyl dl-cis, transclnysanthvmate. D 3-p-chlorophenylthiobenzyl uhrysanthemate...

EXAMPLE 40 0.2 part of the present compound (I), 0.2 part of Tetramethrin were dissolved in a mixture of 7 parts of xylene and 7.6 parts of deodorized kerosene. The solution was filled in an aerosol container. After attaching a valve portion to the container, 85 parts of a propellant (e.g. liquefied petroleum gas) was charged therein under pressure through said valve.

An aerosol was thus obtained.

Starting material EXAMPLE 41 Sodium dl-cis, trauscliyrsunthc1nate F 0.4 part of the present compound (4) was dissolved in a mixture of 7 parts of xylene and 7.6 parts of deodorized kerosene under stirring. An aerosol was thus obtained from the solution by the procedures as described in Example 40.

EXAMPLE 42 0.3 part of the present compound (6) and 0.3 part of Fenitrothion were dissolved in a mixture of 7 parts of xylene and 7.4 parts deodorized kerosene with stirring. An aerosol was thus obtained from the solution according to the 75 procedures as described in Example 40.

ate. 3-o-tn1ylthiobenzylalcohoL dl'cis, transchrysanmlimic acid chlnride alcohol Example EXAMPLE 43 0.3 part of the present compound (7), 0.2 part of Tetramethrin, 13.5 parts of deodorized kerosene and 1 part of Atmos 300 (a registered trade name for an emulsifier sold by Atlas Chemical Co.) were mixed and added with 50 parts of pure water to make emulsion. The emulsion was filled in an aerosol container together with 35 parts of a mixture of deodorized propane and butane in a ratio of l 3.

A water-based aerosol was thus obtained.

EXAMPLE 44 1 part of the present compounds (1), (4) and (6), respectively, was dissolved in 20 parts of acetone. To the solution, 99 parts of 300 mesh diatomaceous earth were added. The mixtures were thoroughly mixed individually by means of a mortar, and acetone was evaporated. Three dusts were thus obtained, respectively.

EXAMPLE 45 EXAMPLE 46 To an uniform mixture of 25 parts of the present compound (4) and parts of Sorpol SM-200, 70 parts of 300 mesh talc were added and thoroughly mixed by means of a mortar. A wettable powder was thus obtained.

EXAMPLE 47 1.5 g ofthe present compounds (9), (1 1), (l2), (13), (14), (l7), (19), (21) and (22), respectively, were dissolved in 20 ml.of methanol, and the solutions were mixed homogeneously with 98.5 g of the mosquito coil carrier as described in Example 39, and methanol was evaporated. The residues were added with 150 ml of water, thoroughly kneaded, shaped into mosquito coil and dried. Nine mosquito coils each containing 1.5 per cent by weight of the active ingredients were thus obtained, respectively.

EXAMPLE 48 0.2 part of each ofthe present compounds (26), (27), (28), (30) and (32), respectively, was dissolved in kerosene to make 100 parts, whereby a corresponding oil spray was obtained.

EXAMPLE 49 A mixture of 0.1 part of the present compound (29) and 0.4 part of piperonyl butoxide was dissolved in kerosene to make 100 parts, whereby an oil spray was obtained.

EXAMPLE 50 A mixture of 0.1 part of the present compound (31) and 0.4 part of sulfoxide was dissolved in kerosene to make 100 parts, whereby an oil spray was obtained.

EXAMPLE 51 A mixture of 0.1 part of the present compound (33) and 0.4 part of MGK-264 was dissolved in kerosene to make 100 parts, whereby an oil spray was obtained.

EXAMPLE 52 A mixture of parts of the present compound (26), 3 parts of DDVP, 10 parts of Sorpol SM-200 (registered trade mark 'was charged therein under for an emulsifier produced by Toho Chemical Co.) and 72 parts of xylene was thoroughly stirred to obtain an emulsifiable concentrate.

EXAMPLE 5 3 A mixture of 20 parts of each of the present compounds (29), (31) and (33), 10 parts of Sorpol SM-2OO and 70 parts of xylene was thoroughly stirred to obtain a corresponding 20 percent emulsifiable concentrate.

EXAMPLE 54 A solution of 1 part of each of d-trans-chrysanthemate of the present compound (26) and the present compound (27) in 20 ml of methanol was homogeneously stirred and mixed with 99 parts of a mosquito coil carrier (a 315:1 mixture of Tabu powder, pyrethrum mare and wood powder). After vaporizing the methanol, the mixture was thoroughly kneaded with 150 ml of water and was then dried to obtain a corresponding 1 percent mosquito coil.

EXAMPLE 55 0.3 part of the present compound (26), 0.2 part of tetramethrin, 0.5 part of methoxychlor, 7 parts of xylene and 7 parts of deodorized kerosene were thoroughly mixed and dissolved together. The thus obtained solution was charged into an aerosol container. After attaching a valve portion to the container, parts of a propellant (liquefied petroleum gas) pressure through said valve portion to obtain an aerosol.

EXAMPLE 5 6 0.3 part of the present compound (28), 0.3 part of Fenitrothion, 7 parts of xylene and 7.4 parts of deodorized kerosene were mixed and dissolved together, and the solution was treated in the same manner as in Example 55 to obtain an aerosol.

EXAMPLE 5 7 A mixture of 0.3 part of the present compound (27), 0.2 part of tetramethrin, 0.5 part of NlA-16388, 2.5 parts of chlorosene Nu (registered trade name for a product of Dow Chemical Co. which contains 1,1,1-trichloroethane as an active ingredient), 5.5 parts of deodorized kerosene and 1 part of the emulsifier Atoms 300 (registered trade name for an emulsifier produced by Atlas Chemical Co.) was emulsified by addition of 45 parts of pure water. Thereafter, the emulsion was charged into an aerosol container together with 45 parts of a 3:1 mixture of deodorized butane and deodorized propane, whereby a water-based aerosol was obtained.

EXAMPLE 58 A mixture of 1 part of each of the present compounds 26) and (28) and 5 parts NlA-16388 was dissolved in 20 parts of acetone. This solution was charged with 94 parts of 300 mesh diatomaceous earth and was thoroughly stirred and mixed in a mortar. Thereafter, the acetone was removed by vaporization to obtain a corresponding dust.

EXAMPLE 59 EXAMPLE 60 25 parts of the present compound 32), SM-200 and 70 parts of 300 mesh talc were 5 parts of Sorpol throughly stirred and mixed together in a mortar to obtain a wettable powder.

The insecticidal efi'ects of the present compositions thus prepared is shown in the following test examples.

TEST EXAMPLE 1 The oil sprays obtained according to Examples 35, 36, 37, 48, 49, SO and 51, respectively, and a 0.2 percent allethrin oil spray as control, were individually sprayed in an amount of 5 ml using Campbels turn table apparatus [Soap and Sanitary Chemicals," Vol. 14, No. 6, 119 1938)].

After seconds from the spray, the shutter was opened, and house-fly adults (about 100 flies per group) were exposed to the mist for 10 minutes and were then transferred to an observation cage. In the cage, the flies were fed and were al- 1 lowed to stand for one day at room temperature. Thereafter, the number of killed flies was counted to calculate the mortality thereof. The results are as shown in Table 2.

TABLE 2 Composition (oil spray) Mortality Example 35... [Containing 0.05% of compound (1)].. 100

Do [Containing 0.05% of compound (4)]- 07 Do [Containing 0.05% of compound (6)].. 92 Example 36... [Containing 0.2% of compound (2) and 0.8% 95 of pioeronyl butoxide]. Do [Containing 0.2% of compound (5) and 0.8% 90 of piperonyl butoxide]. Do [Containing 0.2% of compound (7) and 0.8% 87 01 piperonyl butoxide]. Do [Containing 0.2% of compound (8) and 0.8% 75 of piperonyl hutoxide]. Do [Containing 0.2% of compound (10) and 0.8% 93 of piperonyl butoxide]. Example 37.. [Containing 0.2% ofcompound (16) and 0.8% 100 01' NlA-1fi338l. D0 [(ontniningOflZ. of compound (20) and 0.8% 05" of NlA-1638Sl. Exnmplc 1S... [Containing 0.2% of compound (20)l...-... 08 Do. [(ontniuing. 0.2% of conmouud (27)].. 87 Do. [(ontnining 0.2Z-Zofco1nponmi (28)[ 82 Do [(ontnining 0.2% of compound (30)]. 80 Do. ltontniuing 0.2% of cmnpound (32)].. 85 Exmnplo 40. [Containing 0.1%ofconmouud (211) nn 10 A, 00

of [)lpm'mlyl hnloxidv]. 0 Examplc fill [f ontnininul).1",,oft-unwound (31) and 0.4% 15 4 of sull'oxidul. Example 51 [Containing 0.1 ol'cxmmnluul (83) :m 10.4,. 87

of MG K-Zi l. Allnlhrin 0.2% 011 spray 84 TEST EXAMPLE 2 The emulsifiable concentrates formulated according to Example 38, 52 and 53 were respectively diluted with water to 40,000 times. 1.5 liters of the thus prepared test emulsions were charged in a styrol case of 23 cm X 30 cm with a depth of 6 cm. Into the case, about 100 larvae of northern house mosquitoes were liberated, whereby 90 percent or more of the larvae could be killed on the next day.

TEST EXAMPLE 3 About 20 northern house mosquito adults were liberated in a (70 cm) glass chamber. Each 1 g of the mosquito coils formulated according to Examples 39, 47 and 54 respectively, each containing the present compounds (1), (4), (5 (6), (9), (11), (12), (13), (14), (17), (19), (21), (22), (27) and dtrans-chrisanthemate of (1), (19) and (26) were ignited on both ends and were individually placed at the center in the chamber. The number of knocked-down insects was counted after 20 minutes and the knock-down percentages were calculated as more than 80 per cent in each test.

TEST EXAMPLE 4 The insecticidal effects on housefly adults of the aerosols fonnulated according to Examples 40, 41, 42, 43, 55, S6 and 57 were tested by the aerosol test method using Peer Grady's chamber [the method disclosed in Soap and Chemical Spe cialties, Blue Book." (1965)]. The results are as shown in Table 3.

TABLE 3 Sprayed Knock-down ratio percent 10 liters of water was poured into a 14 liters polypropylene bucket. Into the water, the granular preparation formulated 5 according to Examples 45 and 59 was charged in an amount of 1 g. After 1 day, 100 full grown northern house mosquito larvae were liberated in the water, whereby more than per cent of the larvae could be killed within 24 hours.

TEST EXAMPLE 6 A glass Petri dish of 14 cm in inner diameter and 7 cm in height was coated on the inner wall with butter, leaving at the lower part an uncoated portion of 1 cm in height. Onto the bottom of the dish, the dusts each containing the compound (1), (4), (26) and (28) fomulated according to Examples 44 and 58 were uniformly dusted individually in a proportion of 2 g/m Subsequently, 10 German cockroach adults were liberated in the dish and were contacted with the individual dusts for 30 minutes. After 1 day, more than 90 percent of the cockroaches were knocked-down and after 3 days, more than 90 percent of the insects could be killed.

TEST EXAMPLE 7 1n 1/50,000 Wagner pots were grown rice plants which had elapsed 45 days after sowing. The emulsifiable concentrates containing the compounds 1), (6) and (30), respectively, obtained according to Examples 38 and 53, and the wettable powder formulated according to Example 46 was diluted in-' dividually with water to 400 times. The thus prepared test liquid were individually sprayed out the rice plants in a proportion of 10 ml per pot, and each pot was covered with wire net. into the net, 30 adults of green rice leaf hoppers were liberated. After 24 hours, more than 90 percent of the hoppers could be killed in all cases.

What we claimed is:

1. A compound of the formula CH2OCCH C/ Y o R2 a)m 01: 3 3

wherein Y is oxygen or sulfur, R, is hydrogen or methyl, R is methyl, 2-methyl-l-propenyl or 2-methoxycarbonyl-l-propenyl when R is hydrogen, or methyl when R is methyl, R and R are the same or different and are halogen or methyl and m is 0 or an integer or 1 to 3, and n is O or an integer of 1 to 2.

2. A compound according to claim 1, wherein R is hydrogen and R is 2-methyll -propenyl.

3. A compound according to claim 2, wherein Y is oxygen.

4. A compound according to claim 1, wherein R and R are methyl, respectively.

5. A compound according to claim 4, wherein Y is oxygen.

6. A compound according to claim 1, wherein Y is sulfur.

7. A compound of the formula 8. A compound ofthe formula 9. A compound of the formula UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 666 789 Dated May 30 1972 ITAYA et al Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Columns l3 l4, Example 22, the starting material should read -dl-cis, transand not "d-cis, trans" Signed and sealed this 9th day of July 1974.

(SEAL) Attest:

MCCOY M. GIBSON, JR. C MARSHALL DANN Attesting Officer Commissioner of Patents FORM po'wso USCOMM-DC wave-P09 i ".5. GOVERNMENT IIINYING OFFICE 1 I969 0-?66-334 UNl'lED STA'EES PA'l'l'lNT OFFICE CEiTlFICATE OF CURRECTIUN Pat nt N 3,666,789 Dated May 30, 1972 Inventor(s) Itaya et al.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Please make the following corrections:

In Section [72] change the spelling of the seventh inventor s name to read Keimei Fujimoto-.

Please insert the following missing claim for priority:

Signed and sealed this 6th day of February 1973.

( AL) Attest:

EDWARD M.FLETCHER,JRQ

' ROBERT GOT'I' Attesting Officer SCHALK Commissioner of Patents ORM PO-IOSO (10-69) USCOMM-DC BO376-PG9 Q U.S. GOVERNMENT PRINTING OFFICI (96S 0-366-334 

2. A compound according to claim 1, wherein R1 is hydrogen and R2 is 2-methyl-1-propenyl.
 3. A compound according to claim 2, wherein Y is oxygen.
 4. A compound according to claim 1, wherein R1 and R2 are methyl, respectively.
 5. A compound according to claim 4, wherein Y is oxygen.
 6. A compound according to claim 1, wherein Y is sulfur.
 7. A compound of the formula
 8. A compound of the formula
 9. A compound of the formula 